The demand for sustainable energy storage solutions has led to increased interest in biomass-derived carbon aerogels as electrode materials for supercapacitors. These materials offer a high surface area, tunable porosity, and excellent electrochemical properties while utilizing renewable and waste biomass sources. This study evaluates the electrochemical performance of various biomass-based carbon aerogels, including those derived from cellulose, lignin, chitosan, and biomass waste, to identify key factors influencing supercapacitor efficiency. Principal Component Analysis (PCA) is employed to systematically analyze the relationships between structural and electrochemical properties, such as the specific surface area, specific capacitance, capacity retention, rate capability, energy density, and power density. The PCA results indicate that the first two principal components (PC1 and PC2) explain 58.20% of the total variance, with capacity retention (26.22%), energy density (19.55%), and specific capacitance (18.48%) identified as the most critical quantitative factors influencing supercapacitor performance. Chitosan-derived carbon aerogels exhibit superior capacitance and energy density, with a specific capacitance reaching up to 1074 F/g and energy density of 40.18 Wh/kg, whereas lignin-based aerogels demonstrate a high structural stability and capacity retention (up to 97.4%). Biomass waste-derived aerogels, despite their lower performance (176–298.6 F/g capacitance, 81.6–91.7% retention), provide cost-effective and environmentally sustainable alternatives. This quantitative analysis offers valuable insights into the rational design of high-performance, biomass-based aerogels, contributing significantly to the development of sustainable energy storage technologies.